以抗<strong>CMAS</strong>腐蚀为目标的稀土硅酸盐环境障涂层高熵化设计与性能提升

doi:10.11900/0412.1961.2022.00556

金属学报

2023, Vol. 59

Issue (4): 523-536 DOI: 10.11900/0412.1961.2022.00556

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以抗CMAS腐蚀为目标的稀土硅酸盐环境障涂层高熵化设计与性能提升

王京阳(

), 孙鲁超, 罗颐秀, 田志林, 任孝旻, 张洁

中国科学院金属研究所沈阳材料科学国家研究中心沈阳 110016

Rare Earth Silicate Environmental Barrier Coating Material: High-Entropy Design and Resistance to CMAS Corrosion

WANG Jingyang(

), SUN Luchao, LUO Yixiu, TIAN Zhilin, REN Xiaomin, ZHANG Jie

Shenyang National Laboratory for Materials Science, Institute of Metal Research, Chinese Academy of Sciences, Shenyang 110016, China

引用本文:

王京阳, 孙鲁超, 罗颐秀, 田志林, 任孝旻, 张洁. 以抗CMAS腐蚀为目标的稀土硅酸盐环境障涂层高熵化设计与性能提升[J]. 金属学报, 2023, 59(4): 523-536.
Jingyang WANG, Luchao SUN, Yixiu LUO, Zhilin TIAN, Xiaomin REN, Jie ZHANG. Rare Earth Silicate Environmental Barrier Coating Material: High-Entropy Design and Resistance to CMAS Corrosion[J]. Acta Metall Sin, 2023, 59(4): 523-536.

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摘要:

环境障涂层是大推力和高推重比航空发动机的关键材料，能够为碳化硅纤维增强碳化硅(SiC_f/SiC)陶瓷基复合材料热端部件提供有效防护，阻挡燃气及环境腐蚀介质的侵蚀。稀土硅酸盐具有与SiC基复合材料匹配的热膨胀系数以及良好的化学相容性，是目前国际公认的优选环境障涂层体系。然而，目前已知稀土硅酸盐材料耐典型低熔点氧化物CaO-MgO-Al₂O₃-SiO₂ (CMAS)腐蚀性能不足，难以满足新一代航空发动机1300℃及以上温度的工程应用需求。本文总结了近年来稀土硅酸盐耐CMAS腐蚀相关研究进展，重点介绍了本团队关于单一稀土主元单/双硅酸盐CMAS腐蚀机理的研究成果，以此为基础提出高熵化设计思路，旨在充分利用不同稀土元素在与CMAS反应过程中呈现的特性差异，通过合理设计多稀土主元搭配实现稀土硅酸盐材料耐CMAS腐蚀性能提升。最后对高熵稀土硅酸盐环境障涂层的发展方向进行了展望。

关键词 ：环境障涂层, 稀土硅酸盐, 高熵陶瓷, CMAS腐蚀

Abstract：

High thrust-to-weight ratios and high propulsion are necessary requirements for revolutionizing the aviation technology. Emerging hot-section engine components are currently focused on SiC_f/SiC ceramic matrix composite materials, wherein the environmental barrier coatings (EBCs) are needed to protect the engine components from the harsh combustion environment. Due to their matched thermal expansion coefficient and good chemical compatibility with the SiC_f/SiC ceramic matrix composites substrates, rare earth (RE) silicates have been identified as promising EBC materials. However, they cannot provide reliable protection for the engine components when the working temperature rises over 1300^oC, mainly because of their poor resistance to the low melting point oxides CaO-MgO-Al₂O₃-SiO₂ (CMAS) melts. This review discusses the current state of research on the CMAS corrosion resistance of RE silicates. First, the interaction and degradation mechanisms of single-RE-component RE₂SiO₅ and RE₂Si₂O₇ are discussed, and the different roles of RE species in reacting with CMAS melts are summarized. Then, the concept of high-entropy design is introduced, enabling synergistic optimization of the effects of multiple RE species in terms of CMAS resistance, by delicately designing the multi-RE-component (nRE _x ) compositions. Such a strategy leads to enhanced CMAS corrosion resistance in some novel (nRE _x )₂SiO₅ and (nRE _x )₂Si₂O₇ materials. Finally, potential prospects, opportunities, and challenges for high-entropy RE silicates as EBC materials are discussed.

Key words： environmental barrier coating rare earth silicate high-entropy ceramic CMAS corrosion

收稿日期: 2022-11-01

ZTFLH:

TB32

基金资助:国家自然科学基金项目(U21A2063);国家自然科学基金项目(52002376);国家重点研发计划项目(2021YFB3702300);国家科技重大专项项目(2017-VI-0020-0093);中国科学院重点部署项目(ZDRW-CN-2021-2-2);辽宁省“兴辽英才计划”项目(XLYC200-2018)

通讯作者: 王京阳，jywang@imr.ac.cn，主要从事极端环境用陶瓷及复合材料研究

Corresponding author: WANG Jingyang, professor, Tel: (024)23971762, E-mail: jywang@imr.ac.cn

作者简介: 王京阳，男，1971年生，研究员，博士

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图1 Tb2SiO5、Er2SiO5和Tm2SiO5在1300℃低熔点氧化物CaO-MgO-Al2O3-SiO2 (CMAS)腐蚀50 h之后的截面形貌、反应区局部形貌和截面EDS面扫描的元素分布，以及表面形貌和XRD谱[21]

图2 3类稀土单硅酸盐(RE2SiO5) 1300℃ CMAS腐蚀50 h反应示意图[21]

图3 (Y1/4Ho1/4Er1/4Yb1/4)2SiO5的TEM明场像、原子分辨率[010]方向的高角环形暗场(HAADF)像及对应的Fourier变换衍射图、模拟的X2-RE2SiO5 [010]晶带轴方向的结构示意图及对应的元素分布EDS扫描图[42]

图4 四元(4RE1/4)2SiO5在1300℃下CMAS腐蚀50 h后样品表面XRD谱、腐蚀后样品表面形貌、腐蚀后样品截面残余CMAS析出空心棒状磷灰石形貌以及腐蚀后样品截面反应析出层放大图[42]

表1 (4RE1/4)2SiO5在1500℃下CMAS腐蚀4 h后反应析出层和冷却析出层的磷灰石相中稀土元素RE与Ca的EDS定量分析结果[41] (atomic fraction / %)

图5 高熵稀土双硅酸盐(Er0.25Tm0.25Yb0.25Lu0.25)2Si2O7经1500℃ CMAS腐蚀反应4和50 h后样品截面的电子探针元素分析，以及单稀土主元双硅酸盐Yb2Si2O7和Lu2Si2O7经1500℃ CMAS腐蚀25 h后截面形貌[45]

图6 高熵稀土双硅酸盐(Er0.25Tm0.25Yb0.25Lu0.25)2Si2O7 1500℃ CMAS腐蚀机制示意图[45]

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